Modification of alkyd resin compositions with meta-bromo benzoic acids



United States Patent MODIFICATION OF ALKYD RESIN COMP OSI- A TIONS WITH META-BROMO BENZOIC ACIDS Raymond L. Heinrich, Baytown, Tex., and David A. Berry and Richard J. Dick, Columbus, Ohio, assignors, by direct and mesne assignments, to Esso Research and Engineering Company, Elizabeth, N.J., a corporation of Delaware No Drawing. Filed Aug. 28, 1958, Ser. No. 757,692

3 Claims. (Cl. 26022) This invention relates to modified alkyd resins. More particularly, this invention relates to modified alkyd resins of improved hardness and drying characteristics. Alkyd resins are widely used in the preparation of surface coating compositions. A particularly desired class of alkyd resins are the so-called oilmodified alkyd resins employed in coatings and prepared by the intercondensation of a polybasic acid (preferably dibasic), a polyol, and an unsaturated fatty acid.

The present invention is directed to a discovery in the field of oil-modified alkyd resins which not only permits the. inclusion of m-bromobenzoic acid as a raw material but which also provides oil-modified alkyd resins of improved physical and chemical properties.

It has now been discovered that alkyd resin compositions of improved physical properties may be obtained by replacing from about 55 to about 65 mol percent of the fatty acid component of the alkyd resin with mbromobenzoic acid. In particular, the alkyd resin coating compositions of the present invention are characterized by satisfactory drying times and the films prepared therefrom are characterized by excellent flexibility and hardness.

Alkyd resin chemistry is well known to those skilled in the art and, in the interest of brevity, will not be discussed in detail. The preparation and physical properties of alkyd resins are described in numerous texts, such as vol. I of Organic Coating Technology, Henry Fleming Payne, John Wiley and Sons, 'Inc., N.Y., 1954.

Although a wide variety of polybasic acids such as phthalic anhydride, isophthalic acid, succinic acid, 2.2.1- bicyclo endomethylene-7-heptene-2,3-dicarboxylic acid, etc., may be utilized, the preferred acid is generally phthalic anhydride. Similarly, although a wide variety of polyols such as glycerol, trimethylol propane, pentaerythritol, sorbitol, mannitol, etc. may be utilized, the preferred polyol is generally glycerol. The polyol should contain an average of from about 2.5 to about 4.5 hydroxyl groups per molecule and, preferably, about 3 hydroxyl groups per molecule.

A wide variety of unsaturated fatty acids may be utilized in the preparation of modified alkyd resins, the source of the fatty acid normally being a naturally occurring vegetable or marine oil such as linseed oil, soybean oil, tall oil, menhaden oil, tung oil, castor oil, etc.

Frequently, minor amounts of additional components such as maleic anhydride, dimerized or bodied fatty acids, saturated fatty acids, etc. will also be utilized.

In general, the polybasic acid, polyol, and fatty acid are interreacted in proportions sufiicient to provide about a to 25 weight percent excess of polyol. Excess polyol may be defined as that amount of polyol in excess of the amount necessary to combine with the sum of the acid groups in the fatty acid and the polybasic acid on a theoretical basis. Alkyd resins are conventionally characterized as short oil modified alkyd resins, medium oil alkyd resins, and long oil alkyd resins, depending upon 'ice mol equivalents of polyol with about 2 mol equivalents of polycarboxylic acid and 1 mol equivalent of unsaturated fatty acid. Progressively larger amounts of polycarboxylic acid and'progressively smaller amounts of unsaturated fatty acid are utilized to provide for a shorter oil length. Thus, short oil alkyd resins may be prepared by the intercondensation of about 3.1 to about 3.4. mol equivalents of polyol with about 2.3 to about 2.5 mol equivalents of polycarboxylic acid and from about 0.7"to about 0.5 mol equivalents of unsaturated fatty acid.

Accordingly, the alkyd resin compositions of the present invention may be defined as intercondensation products of about 3.1 to about 3.4 mol equivalents of a polyol containing about 2.5 to 4.5 hydroxyl groups per molecule with about-2 to 2.5 mol equivalents ofa polycarboxylic acid and about 1 to about 0.5 mol equivalents long oil alkyd resins.

The invention will be further illustrated by the following specific examples which are given by way of illustration and not as limitations on the scope of this invention.

EXAMPLE I A plurality of alkyd resins were prepared utilizing phthalic anhydride, glycerol, soya fatty acids, and a variety of halogenated monocarboxylic aromatic acids.

A plurality of alkyd resins were prepared utilizing phthalic anhydride, glycerol, an unsaturated fatty acid and, except for the base resin, an aromatic monocarboxylic acid. In preparing the base resin, about 60 weight percent of fatty acid was utilized. The amount of fatty acid utilized in preparing the other resins was less, the amount used being determined by the extent to which the fatty acid Was replaced, on a molar basis, by the aromatic monocarboxylic acid. A 6.7 percent molar excess of glycerol was used in order to obtain equivalent degrees of polymerization. v

All of the ingredients were charged at once to a flask fitted with a reflux condenser connected to a Dean-Stark tube. The charge was heated to a temperature of about 450 F. over a 3 to 4 hour period and maintained at this temperature for about 5 to 3 hours. An atmosphere of refluxing xylene vapor was maintained over the cook and vigorous agitation was employed. The final acid numher was Within the range of about 6.5 to 8.5. Water was azeotropically removed as evolved during the course of the reaction.

In Table I there is listed the aromatic monocarboxylic acid modifiers employed, the extent to which the fatty acid was replaced with the acid modifier on a mol percent basis, and the weight percent of acid modifier utilized, based upon the total charge. In addition, the drying time of the alkyd resins prepared in the above-described fashion is given, together with the hardness of films prepared by drying of the alkyd resin compositions. The drier concentration employed for the air drying .tests was about 0.5 weight percent of lead and about 0.05 weight percent of cobalt, based on the weight of the resin solids, and was added to the alkyd resin as a solution of cobalt and lead naphthenate. For the baked film tests, the cobalt salt was employed in an amount sufiicient to provide 0.02 weight percent cobalt.

Table l m-Chlorobenzolc and Anhydride-Glycerln Alkyds m-Bromobeuzoic Acids as Modifiers in Soya-Phthalio 1 Approximately 62 percent oil length.

From Table I it will be observed that unpredictably improved results were obtained through the use of m-bromobenzoic acid as compared withthe chlorobenzoic acids, with respect to compositions containing 55 to 65 mol percent replacement of fatty acid. In this case, the composition had a significantly faster drying time and the resultant film had a significantly greater swaid hardness.

Having thus described our invention, what is claimed is: r

1. An alkyd resin composition comprising the intercondensation product of about 3.1 to about 3.4 mol equivalents of a polyol containing an average of from about 2.5 to 4.5 hydroxyl groups per molecule with from about 2 to 2.5 mol equivalents of a polycarboxylic acid and, correspondingly, from about 1 to about 0.5 mol equivalents of a modifier portion consisting of about 35 to 45 mol percent of an unsaturated glyceride ,oil fattyv acids portion and, correspondingly, about 65 to 55 mol percent of m-brornobenzoic acid.

2. An alkyd resin coating composition as in claim 1 wherein the polyol is glycerol and the polycarboxylic acid is a phthalic acid,

3, An alkyd resin coating composition as in claim 1 wherein the polyol is glycerol, the polycarboxylic acid is a phthalic acid, and the fatty acids are soya fatty acids,

References Cited in the file of this patent UNITED STATES PATENTS 1,950,468 Zwilgmeyer Mar. 13, 1934 2,056,656 Ellis Oct. 6, 1936 2,087,852 Ellis July 20, 1937 2,606,161 Marling Aug. 5, 1952 2,618,616 Tess et a1. Nov. 18, 1952 2,915,488 Kraft et a1. Dec. 1, 1959 

1. AN ALKYD RESIN COMPOSITION COMPRISING THE INTERCONDENSATION PRODUCT OF ABOUT 3.1 TO ABOUT 3.4 MOL EQUIVALENTS OF A POLYOL CONTAINING AN AVERAGE OF FROM ABOUT 2.5 TO 4.5 HYDROXYL GROUPS PER MOLECULE WITH FROM ABOUT 2 TO 2.5 MOL EQUIVALENTS OF A POLYCARBOXYLIC ACID AND, CORRESPONDINGLY, FROM ABOUT 1 TO ABOUT 0.5 MOL EQUIVALENTS OF A MODIFIER PORTION CONSISTING OF ABOUT 35 TO 45 MOL PERCENT OF AN UNSATURATED GLYCERIDE OIL FATTY ACIDS PORTION AND, CORRESPONDINGLY, ABOUT 65 TO 55 MOL PERCENT OF M-BROMOBENZOIC ACID. 